Adducts of a quaternary ammonium salt with a phenol



United States Patent 3,328,437 ADDUCTS OF A QUATERNARY AMMONiUM SALT WITH A PHENOL Richard M. Lee, deceased, late of Leominster, Mass, by Mary G. Lee, sole legatee, Louisville, Ky., and Richard G. McAllister, Leominster, Mass, assignors to The Borden Company, New York, N.Y., a corporation of New Jersey N0 Drawing. Continuation of application Ser. No. 179,454, Mar. 13, 1962. This application Feb. 1, 1966, Ser. No. 525,220

4 Claims. (Cl. 260-404) This is a continuation application of application Ser. No. 179,454, filed Mar. 13, 1962, now abandoned.

This invention relates to an antistatic material and to resin compositions containing the said material.

The invention is particularly useful in preventing the accumulation of or accelerating leakage of electric charges in sound records, coating for fabrics and the like and will be illustrated by description in connection with such use.

Quaternary ammonium compounds have been used extensively for this purpose. Certain disadvantages have persisted, however, in their use. Quaternary ammonium salts such as Catanac SN, for example, when incorporated directly into a composition for phonograph records in amounts needed to impart desirable antistatic properties, cause excessive lubricity of the composition and thus retard dispersion of the various components in the composition during milling. Mixing of the salt in advance with the resin constituting the base material, i.e., before the stage of compounding the composition on the usual heated mixing rollers, has been proposed as means of decreasing such over-lubrication and shortening the subsequent milling cycle.

The present invention provides an antistatic material that (1) is dispersible with satisfactory results in the resin at the compounding stage, (2) avoids over-lubricity in the compounded composition, (3) is etfective in proportion less than the amount of the relatively expensive quaternary component required previously, and (4) minimizes the discoloration, especially of vinyl chloride homopolymers and copolymers, which is caused by larger amounts of the quaternary salt.

Briefly stated, the invention comprises the herein described process and product of heating a mixture consisting essentially of a quaternary ammonium salt with a phenol. The invention comprises also the blend of the product of the said heating with a resin and to the resulting antistatic compositions and articles made therefrom.

As the resin or base material to be made antistatic there is used any of the polymers of ethenoid monomers commonly employed in making sound records, coatings for fabrics or automobile seat covers as, for example, a polyvinyl chloride resin, polystyrene or polyvinylidene chloride. The vinyl chloride resin may be the homopolymer or the copolymers of vinyl chloride as the component in major amount, such as 50%-98% of the copolymer, with such other copoly-rnerizable ethenoid monomers as vinyl acetate, butyrate, and stearate and methyl and ethyl or other C C, alkyl esters of acrylic or methacrylic acids. A particularly suitable copolymer is one containing about 83%88% of vinyl chloride and 1'7%l2% of vinyl acetate for 100 parts total. The styrene resin may be the homopolymer of styrene or alpha-methylstyrene.

The phenol used is ordinarily bisphenol A, that is 2,2- bis (p-hydroxyphenyl)propane. Other phenols that can be used in place of the bisphenol A are p-tert. butyl phenol, p-phenyl phenol, bis(p-hydroxyphenyl) methanepmd 4,4- dihydroxy bisphenyl. The hydroxyl group of the aromatic Patented June 27, 1967 nucleus of the phenol must be free, i.e., unsubstituted to make the phenol operative. Phenol others, for example, are inoperative for our purpose.

As the quaternary we use any water soluble quaternary ammonium compound that alone is effective in causing discharge of static electricity from plastics, e.g., as an antistatic agent.

The compound used is ordinarily a quaternary salt containing at least 2 C -C alkyl groups which preferably are both methyl and 2 other monovalent radicals that may be alkyl, aryl, alkaryl, aralkyl or oxy-substitution products thereof. The union of the salt may be a halide, sulfate, hydrogen sulfate, phosphate, hydrogen phosphate or the like. Examples of such quaternaries that we use are Catanac SN (dimethyl stearamidopropyl 2-hydroxyethyl ammonium nitrate), Catanac SP (dimethyl stearamidopropyl 2 hydroxyethyl ammonium dihydrogen phosphate), Cetol (cetyl dime-thyl benzyl ammonium chloride), Ammonyx 4002 (stearyl dimethyl benzyl ammonium chloride), cetyl diethyl benzyl ammonium chloride, Arquad 12-50, triethyl alkyl ammonium chloride, the alkyl being mixed dodecyl and tetradecyl, and Hyamine 1622 (diisobutylphenoxyethoxyethyl dimethyl benzyl ammonium chloride) In addition to the phenol and the quaternaries, we can introduce various conventional materials for their usual purposes that are without substantial eifect on the antistatic property of the product. Thus the selected resin may be in a blend with the phenol during the heating with the quaternary, as the resin admixture at this stage does not affect adversely the functioning of the phenol and quaternary. Also we may use conventional stabilizers for the resin, as, for instance, the combination of triphenyl phosphite and the laurate of barium, cadmium, or like metal, d-ibasic lead stearate and tetra'basic lead fumarate; and pigmentary or dye materials of nature commonly used in the articles of the kind to be made. Plasticizers are not required in sound records. For other purposes dibutyl or dioctyl phthalate, tricresyl phosphate or other non-volatile solvent that is a conventional plasticizer for the resin selected may be incorporated in usual amounts.

The conventional materials, if introduced at all, are in proportions that are usual for the particular purpose for which the composition is being made as, for example, l-6 parts of vinyl resin stabilizer for parts of the polyvinyl chloride resin.

Proportions of the critical materials that are to be used are shown in the following table.

The selected phenol and quaternary ammonium com pound are used suitably in approximately equivalent proportions. When the two components are heated together in the equivalent ratio, the 'adduct obtained is completely soluble in water Whereas bisphenol A by itself, for example, dissolves only to the extent of 0.1% in water. If an excess of phenol over the quaternary salt is used, the excess phenol remains insoluble in water.

Equivalent ratios are 1 mole of the quaternary for 1 of the phenol when the anion of the quaternary salt is monovalent, /2 mole of the quaternary when the anion is divalent, etc. When such reaction giving water solubility to the phenol is not necessary, we can use 14 equivalents of either the phenol or the quaternary ammonium compound for 1 equivalent of the other.

The proportion recommended is at least an equivalent weight of the quaternary for each mole of the phenol that is to be made miscible in cold water.

so developed being observed with an electrometer. When a predetermined level of charge has been reached, the motor is stopped and the decay time noted as a measure of the leakage rate.

The molded stock made as described in this example A ratio that causes reaction of a sufficient proportion 5 accumulated no observable electrostatic charge during to the phenol for sound record compositions is 2 moles the brushing. The stock, consequently, must be considered of the phenol for each mole of the quaternary ammonium as 100% antistatic at the relative humidity then prevailcompound in which the anion is that of a monovalent ing which is estimated at 30%40%. group, e.g., chloride or nitrate. Another test for antistatic properties known as the As to conditions, we heat the selected phenol and cigarette ash test is as follows: The surface of the molded quaternary ammonium compound to a temperature to slab is rubbed 50 times with a cloth and immediately cause complete solution of one in the other, as to between passed about /2 inch above a bed of finely divided 1009-200" C. for a period of about 2 hours or for a cigarette ash. A sample having no antistatic properties shorter or longer period depending upon the exact tem- Will be covered with ash. A sample having excellent ant1 perature of heating and components selected. The heatstatic properties will show no pick-up of ashes. ing time is that required at the temperature used to con- The molded stock above showed no pick-up of ash in vert a representative phenol such as bisphenol A and a this cigarette ash test. representative quaternary salt such as Catanac SN to a The molded, pressed stock including the product of thick viscous oil. When equimolecular proportions of the heating the bisphenol A with Catanac SN also exhibited phenol and the quaternary with monovalent anion are desirable processing characteristics, absence of excess used, the mixture is heated until the entire composition is lubricity during processing, good compatibility of the water-soluble. No further substantial change of viscosity compounded components over a wide range of temperaor properties of the product would occur on further heattures, and better color than a molded slab using the ing. When an excess of phenol is used over the quaternary quaternary salt only as the antistatic agent. present, the mixture is heated until the only precipitation The table below shows some of the results obtained notedin an aqueous solution of the mass isthe amount with our agent, here referred to as an adduct, test 2 and of phenol used in excess of 1 mole for 1 mole of the 3 being included only for contrast. quaternary salt.

Run Antistatic Antistatic Processing No. Antistatic Agent Agent, Percent Properties Properties 0r Resin 1 Adduct of Catanac SN and his 1.2 Excellent Excellent.

phenol AA CatanacSN 1.2 do Poor. Catanac SN preabsorbed on the 1. 2 do Good.

1 Added on the mill, not preabsorbed on the resin.

The quaternar ammonium compound and the selected phenol can be introduced separately into the resin on the compounding rolls and blended thereon, as by hot milling at temperatures of about l00200 C. and preferably 140-170 C. The small amount of acid which deevlops from the polyvinyl chloride resin during this heating accelerates' the desired reaction between the phenol and the quaternary compound. When these two components are premixed in advance and heated to give the desired action of the one upon the other, before incorporation into the resin, it is desirable to add a small amount of an acid catalyst as, for instance, hydrochloric, sulfuric or phosphoric acid as in the proportion of about .001%-0.l% of the total weight of the quaternary and selected phenol. This acid speeds up the desired reaction of the phenol and quaternary Without any adverse effect on the antistatic properties of the compositions.

The inventionwill be further illustrated by detailed description in connection with the following specific examples. In these examples and elsewhere herein, proportions are expressed as parts by weight unless specifically stated to the contrary.

Example 1 mill and molded under pressure into sheets 6 x 6 x 0.075'

inch.

Molded stock is evaluated for antistatic properties by first inducing a surface charge by friction with a brush, as the stock is motor-rotated against the brush, the charge Example 2 An antistatic agent herein called adduct a was prepared separately by heating 1 mole of bisphenol A (228 parts) with '1 mole of Catanac SN (478 parts) with gentle stirring at a temperature of -170 C. After 3 hours heating, the product was a highly viscous liquid (95,000100,000 cps. at 25 C.) with a strong yellow to brown color. There was no separation of the bisphenol A when the product was stirred and dissolved in water to a concentration of 75% by weight at ordinary temperatures. The product was completely miscible in methanol, acetone, and chloroform.

Adduct b was prepared by heating 2 moles of bisphenol A (456 parts) with 1 mole of Catanac SN (478 parts) With gentle stirring at a temperature of 140-170 C., and with 0.01% of 37% hydrochloric acid solution admixed as a catalyst of the action. After 2 hours heating the product was a highly viscous liquid of viscosity 100,- 000 cps. at 25 C., with a strong brown color. When 10 parts 'of adduct b was mixed with 100 parts of water, a white precipitate appeared. This was collected and dried, to give 2.4 parts of a white powder of melting point C. (Bisphenol A melts at 152 C.) The phenol in excess of 1 mole for 1 of the quaternary in adduct b is thus seen to have been unreacted with the quaternary salt and to remain insoluble. This adduct, while only partially miscible in water, is completely miscible in methanol, chloroform, acetone, and ether.

Additive c was prepared by the process steps described above for adduct a except as noted to the contrary. T hus,

Adduct d was prepared as described above for adduct a except that the materials heated were 2 moles (300 parts) of para-t-butyl phenol and 1 mole (478 parts) of Catanac SN. The physical and solubility properties of the product were similar to those of adduct b. 5

Adduct e was prepared by the process steps used above for adduct a except that 1 mole (228 parts) of bisphenol A and 1 mole (447.5 parts) of Hyann'ne 1622 (di-isobutylphenoxy ethoxyethyl dimethyl benzyl ammonium chloride) were the components mixed and heated. The physical and solubility properties of adduct e were similar to those of adduct a.

These adducts and the additive were then compounded separately on heated mixing rollers at 140 C. for 5 minutes (unless otherwise noted) in the following composiand of vinyl acetate were dissolved in 1,000 parts of toluene as the solvent. Into this there was then added and dissolved one part of the antistatic material, adduct b, prepared in Example 2. Films of the resulting solution were sprayed and dried, to a final thickness of 1 mil on automobile upholstery fabric. The film when rubbed with a brush as described in Example 1 did not retain any static charge, whatever charge was induced being lost by leakage substantially as rapidly as formed.

In another test, this one outside the invention, a toluene solution of the same concentration of the same copolymer was used in comparable manner except that the antistatic material was omitted. This solution was sprayed on the automobile fabric, the solvent evaporated and the remaining film brushed as described. A pronounced static charge l5 trons. developed. Component: Parts Example 5 Copolymer of vinyl chloride 85 parts, 15 parts The procedure and composition of Example 1 are used with vinyl acetate 96.8 except that the quaternary ammonium salt there used is Dibasic lead stearate 2.0 replaced by an equal weight of dimethyl stearamido- Antistatic adduct or additive 1.2 propyl 2-hydroxyethyl ammonium nitrate and phosphate,

oetyl dimethyl benzyl ammonium chloride, stearyl di- Total 100.0 methyl benzyl ammonium chloride, cetyl diethyl benzyl The stock was then removed from the mill and molded l p Chloride trilthyl alkyl ammonium ch10" under pressure into sheets 6 x 6 x .075 inches and tested f; n g alkyl 5; g? 'ig i for antistatic properties by the tests described in Exama u enoxye oxye y y enzy Plc 1 I momum chloride, used separately and in turn.

The following table showsthe processing properties and Example 6 lz i gg ig gz i ggglg 5 g The procedure and composition of Example 1 are used W1 a e a He or 1 ve on e o welg except that the bisphenol A therein is replaced by an equi- Test Number 1 2 3 4 5 v 6 7 Additive tested None Catanac SN Additive c Adduct a Adduet b Adduetd. Adduct e. Additive made, from Phenol, do None Ethoxylated Bis-ph enol A Para-t. butyl Bisphenol A.

kind. (12330! phenol. Phenol, moles for 1 mole of do do 0.62. 1 2 2 1.

quaternary salt. galilfifgmall'ly t n t do See above Catanac SN" Catanac SN Catanac SN Catanac SN Hyamine 1622.

8.1110 EDS 1081 Ba nk time (min.) 1 1.5- 7.75- 10.0. 1.5- 1.5 1.5- 1.5. Drop throughs required l. 3 3 1 1 1 1. Total time, min 5 10 12 5 "1 s 5. Antistatic Properties:

Charge decay time by 10 0 2-3 0.1 0.1 0.1 1.

eleetrometer, min. Ash test pickup- Yes No. Yes N o No No. Slt. Color of plastic Translucent, Opaque, beige- Translucent, Opaque, ofi- Opaque, ofl- Opaque, ofi- Opaque, olihazy. tan. white. white. white. white.

1 Time required to work a workable sheet on the mill.

2 Number of times the material drops through the mill before adhering and fusing.

The compositions of tests 1, 2 and 3 form no part of this invention, they being used merely for control purposes. Each of these controls either fails in milling characteristics or antistatic properties and in tests 1 and 3 in both. Test 3 is particularly significant. It shows that the phenol which has been ethoxylated, with conversion of the OH group of the phenol to an ether group, was unsatisfactory as a starting material.

The table shows also the relative economy of the compositions compounded with the adducts over that with the relatively expensive Catanac SN alone. In test No. 2, for instance, the proportion of Catanac SN is 1.2% of the plastic whereas the percentages of it in the better compositions of tests 4, 5 and 6 are only 0.81%, 0.62% and 0.70%, respectively.

Example 3 Example 4 A coating composition was made as follows: 100 parts of the copolymer of 85% of vinyl chloride molar amount of p-tert. butyl phenol, p-phenyl phenol, bis(p-hydroxyphenyl) methane, and 4,4'-dihydroxy bisphenyl, used separately and in turn.

Example 7 The procedure and composition of Example 1 are used except that the copolymer of vinyl chloride and vinyl acetate is replaced by an equal weight of vinyl chloride, a copolymer of about 50%98% of vinyl chloride and 50%2% of vinyl acetate, butyrate and stearate, polystyrene, and a polyvinylidene chloride, used separately and in turn.

It will be understood that it is intended to cover all changes and modifications of the examples of the invention herein chosen for the purpose of illustration which do not constitute departures from the spirit and scope of the invention.

We claim:

1. The process of making a product of a phenol and a quaternary ammonium salt which comprises:

(1) forming a mixture of one mole of a phenol selected from the group consisting of:

(a) 2,2'-bis (p-hydroxyphenol propane, (b) p-tert. butyl phenol, (c) p-phenyl phenol, (d) bis(p-hydroxyphenyl)methane, and

7 (e) 4,4'-dihydroxy bisphenyl, with at least one mole of a quaternary ammonium salt containing at least 2C alkyl groups,,said salt being selected from the group consisting of:

(a) dimethyl stearamidopropyl 2-hydroxyethyl ammonium phosphate,

(b) dimethyl stearamidopropyl 2 hydroxyethyl ammonium nitrate,

(c) cetyl dimethyl benzyl ammonium chloride,

((1) cetyl diethyl benzyl ammonium chloride,

(e) stearyl'dimethyl benzyl ammonium chloride,

(f) dimethyl stearamidopropyl 2-hydroxyethyl ammonium dihydrogen phosphate,

(g) triethyl alkyl ammonium chloride in which the said alkyl is a mixture of dodecyl and tetradecyl, and

(h) diisobutylphenoxyethoxyethyl dimethyl benzyl ammonium chloride, and,

(2) heating said mixture in the temperature range between about 100-200 C. to a complete soltuion and until there is no further substantial change in viscosity on continuing the heating.

2. The process of claim 1, wherein:

(1) said phenol is 2,2'-bis(p-hydroxyphenol) propane,

and

(2) said salt is dimethyl stearamidopropyl Z-hydroxyethyl ammonium nitrate.

3. An antistatic agent consisting essentially of the product of:

(1) forming a mixture of one mole of a phenol selected from the group consisting of:

(a) 2,2'-bis (p-hydroxyphenol propane,

(b) p-tert. butyl phenol,

(c) p-phenyl phenol,

8 (d) bis(p-hydroxyphenyl)methane, and (e) 4,4dihydroxy bisphenyl, with at least one mole of a quaternary ammonium salt containing at least 2C alkyl groups, said salt being selected from the group consisting of:

(a) dimethyl stearamidopropyl Z-hydroxyethyl ammonium phosphate, (b) dimethyl stearamidopropyl Z-hydroxyethyl ammonium nitrate, (c) cetyl dimethyl benzyl ammonium chloride, (d) cetyl diethyl benzyl ammonium chloride, (e) stearyl dimethyl benzyl ammonium chloride, (f) dimethyl stearamidopropyl Z-hydroxyethyl ammonium dihydrogen phosphate, (g) triethyl alkyl ammonium chloride in which the said alkyl is a mixture of dodecyl and tetradecyl, and w (h) diisobutylphenoxyethoxyethyl dimethyl benzyl ammonium chloride, and, l (2) heating said mixture in the temperature range between about 100-200 C. to a complete solution and until there is no further substantial change in viscosity on continuing the heating. 4. The antistatic agent of claim 3, wherein: (1) said phenol is 2,2-bis(p-hydroxypheno1) propane,

and (2) said salt is dimethyl stearamidopropyl Z-hydroxyethyl ammonium nitrate.

No references cited.

CHARLES B. PARKER, Primary Examiner.

ANTON H. SUTTO, Assistant Examiner. 

1. THE PROCESS OF MAKING A PRODUCT OF A PHENOL AND A QUATERNARY AMMONIUM SALT WHICH COMPRISES: (1) FORMING A MIXTURE OF ONE MOLE OF A PHENOL SELECTED FROM THE GROUP CONSISTING OF: (A) 2,2''-BIS (P-HYDROXYPHENOL) PROPANE, (B) P-TERT. BUTYL PHENOL, (C) P-PHENYL PHENOL, (D) BIS (P-HYDROXYPHENYL) METHANE, AND (E) 4,4''-DIHYDROXY BISPHENYL, WITH AT LEAST ONE MOLE OF A QUATERNARY AMMONIUM SALT CONTAINING AT LEAST 2C4 ALKYL GROUPS, SAID SALT BEING SELECTED FROM THE GROUP CONSISTING OF: (A) DIMETHYL STEARAMIDOPROPYL 2-HYDROXETHYL AMMONIUM PHOSPHATE, (B) DIMETHYL STEARAMIDOPROPYL 2-HYDROXYETHYL AMMONIUM NITRATE, (C) CETYL DIMETHYL BENZYL AMMONIUM CHLORIDE, (D) CETYL DIETHYL BENZYL AMMONIUM CHLORIDE, (E) STEARYL DIMETHYL BENZYL AMMONIUM CHLORIDE, (F) DIMETHYL STEARAMIDOPROPYL 2-HYDROXYETHYL AMMONIUM DIHYDROGEN PHOSPHATE, (G) TRIETHYL ALKYL AMMONIUM CHLORIDE IN WHICH THE SAID ALKYL IS A MIXTURE OF DODECYL AND TETRADECYL, AND (H) DIISOBUTYLPHENOXYETHOXYETHYL DIMETHYL BENZYL AMMONIUM CHLORIDE, AND, (2) HEATING SAID MIXTURE IN THE TEMPERATURE RANGE BETWEEN ABOUT 100*-200*C. TO A COMPLETE SOLUTION AND UNTIL THERE IS NO FURTHER SUBSTANTIAL CHANGE IN VISCOSITY ON CONTINUING THE HEATING. 